Chemical engineering department Ph. D. Program: Chemical processes engineering Integration of electrically driven membrane separation processes for water treatment and resources recovery Author: Mònica Reig i Amat Supervisors: Oriol Gibert Agulló / José Luis Cortina Pallás Barcelona, December 2016 Escola Tècnica Superior d’Enginyeria Industrial de Barcelona (ETSEIB) Universitat Politècnica de Catalunya – Barcelona Tech Thesis presented to obtain the qualification of Doctor awarded by the Universitat Politècnica de Catalunya – Barcelona Tech
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Chemical engineering department Ph. D. Program: Chemical processes engineering
Integration of electrically driven membrane separation processes for water treatment
and resources recovery
Author: Mònica Reig i Amat Supervisors: Oriol Gibert Agulló / José Luis Cortina Pallás Barcelona, December 2016
Escola Tècnica Superior d’Enginyeria Industrial de Barcelona (ETSEIB)
Universitat Politècnica de Catalunya – Barcelona Tech
Thesis presented to obtain the qualification of Doctor awarded by the Universitat Politècnica de Catalunya – Barcelona Tech
“All is water”
(Thales of Miletus)
Acknowledgments After four years doing the PhD, my life has changed a lot professionally and personally. I was
just a girl that had finished her degree and I was so excited to start working. When I finished
my master thesis, my supervisor José Luis Cortina told me about electrodialysis with bipolar
membranes and I was so excited to know and understand how that technology worked. As
my friend Rocío said, my eyes were plenty of illusion after talking with him. So, my new path
started that day. Now that I am finishing, I remember each moment doing my PhD with
happiness, even though the hard moments that I also had.
Of course, I have to acknowledge the help of a lot of people during this period. First of all, to
my supervisors: José Luis Cortina and Oriol Gibert because they always trust in me to carry
out this project. Thanks for all the discussions, conversations, revisions, questions and
answers that we had together. I have not enough words to acknowledge all the wisdom that
you have transferred me and the patience that you have had with me. I have no reclamations
to you; you always make me feel like home. Also, I have to thank César Valderrama because,
although you were not my supervisor, you have always helped me in everything that I have
needed. And a special mention to Andriy Yaroshchuk who explained me a lot of about
modelling and NF membranes. Thank you very much.
This thesis received support from the Zero-discharge project (CTQ2011-26799) and the
Waste2Product (CTM2014-57302-R) financed by the “Ministerio de Economía y
Competitividad” and the Catalan Government (SGR2014-50-SETRI), Spain. Moreover, my
work was supported by the Spanish Ministry (MINECO) within the scope of the grant BES-
2012-051914. Also, I want to thank the Dow Chemical contribution for the membranes supply.
I want to thank the contribution of Sandra Casas, Yoshinobu Tanaka (IEM Research),
Salvador Asensio (Solvay Ibérica), people from ATLL-El Prat and from CETaqua for the
results discussion and their help when I asked for it. Also, I would like to acknowledge the
contribution to my thesis to some students during the experimental part: Nuria Leiva, Montse
Martinez, Marta Herrera, Edgar Valverde, Carlos Monserrat and Abel Lara. Besides thanks to
Hasan Farrokhzad, Daniel Trillo, Manuel Galindo and Javier Palacios for their help.
I want to thank Professor Bart Van der Bruggen (KU Leuven, Belgium) and Victor Nikonenko
(Kuban State University, Russia) for the opportunity to spend some months in your
department and take care of me such as one student more of your group. During those
periods I learned a lot professionally and personally. Also, thanks to my friends there: Misha,
Natasha, Katia, Carlos, Zoe, Antonio, Anh, Aditi, between all others.
There are some people, who I consider my friends, because they have been supporting me,
helping me and contributing to my thesis. The first person who was next to me was Yolanda.
Since we started the Chemical Engineering Degree we worked together as sisters and we
almost started and finished the thesis at the same time. I have to give a special acknowledge
to Sandra, who has been literally next to me during our thesis, hers and mine. You have been
my office partner since the first day and it is possible to talk about everything with you. Edxon,
Marc, Gerard and Julio Tico have shared the office with me and I have to acknowledge to all
of you your patience to listen to me and survive next to me! Besides, Edxon helped me a lot in
the modelling issues during the thesis. Marc you are not so talkative and I know that next to
me it is difficult to have the opportunity to talk! However, we found a common topic to talk
about: the tv series and since then we speak every day. Gerard was a good and funny
partner. And Julio Tico is the “Catalan of the year” of course, it is impossible to do not laugh
with you. Moreover, Neus, Mahrez, Julio and Xanel have helped me during the thesis. Neus
helped me in my beginnings in the lab, Mahrez always make me feel like a sister for him, Julio
and Xanel arrived later, but in the few months that you have been in the lab you have become
very important. It is impossible to do not gossip and have fun, which is something important to
do in the few moments that you are not focused on the thesis, with all of you (fourth floor
young people). Thanks to Xialei, Aurora and Diana although you are not in the fourth floor
right now. Thanks to all professors in the fourth floor for your help always that I needed it.
There is a long list of people and friends that contributed to my thesis, who I would like to
thanks all.
Last but not least, I want to acknowledge all my family for their support: to my parents Josep
and Rosó because I always get your support to keep studying and I know that you always
want the best for me; to my grandparents because you have listened to me preparing some
presentations in English although you did not understand. To my husband Raul, who design
this beautiful thesis cover, always support and understand me and because of the thesis we
have not been in our honeymoon yet, but I promise you that we will enjoy it soon. To my
brother Jordi and to all my family because all of you believe that I will succeed in my work.
I sincerely think that without everybody’s support, this thesis would not be the same.
Integration of electrically driven membrane separation processes for water treatment and resources recovery
1
Abstract
Nowadays, due to the growing fresh water demand, several processes are used to purify
seawater by means of desalination or industrial brackish water by different treatment
processes. The main limitation of these techniques is the production of rejected brines. For
this reason, new management techniques for brines valorization are being studied to achieve
the maximum water recovery, avoid liquid streams disposal and recover the valuable
compounds from the concentrated streams. In this thesis, four membrane technologies were
used to promote resources recovery, including water, depending on the valorization way of
the concentrated stream: electrodialysis (ED) was used for its concentration, nanofiltration
(NF) for its purification, selectrodialysis (SED) for its ions separation and ED with bipolar
membranes (EDBM) for acid and base production from the brines. The integration of these
membrane techniques provided brines reuse and promoted potential circular economy based
on solutions where a waste is transformed into a resource.
Seawater reverse osmosis (SWRO) brine was treated by ED in order to concentrate NaCl for
the chlor-alkali industry. An ED pilot plant was used to concentrate the brine up to 150-250 g
NaCl/L, depending on temperature and current density conditions. Then, a mathematical
algorithm was developed to predict the concentration evolution during the ED process. The
model was able to describe the NaCl concentration evolution and the energy consumption
taking into account temperature changes and longtime operation. Moreover, monovalent
selective cationic (MVC) membranes were synthetized using several mixtures of
polyvinylidene fluoride (PVDF) and sulfonated PVDF (S-PVDF). Then, surface
polymerization of polyaniline (PANi) doped with p-toluene sulfonic acid (pTSA) or L-valine was
applied in order to improve their cationic monovalent selectivity. Results indicated that sodium
selectivity increased when using doping agents (higher sodium selectivity when using valine
than pTSA) or increasing the voltage applied.
Besides, NF was used as a purification treatment for the SWRO brine. Different membrane
configurations (flat sheet (FS) and spiral wound (SW)) were tested to study ions rejection
behavior. The solution-diffusion-electromigration-film model (SDEFM) was successfully
applied in order to fit the experimental rejections and calculate the membrane permeances to
each ion. Ions rejection and permeances calculated for both membrane configurations were
Abstract
2
similar. These results indicated that lab-scale results could be used for the NF scale up. Also,
the dominant salt effect on the trace ion rejection was determined by means of a FS
membrane indicating that a higher initial dominant salt concentration implied a lower rejection
for the dominant salt itself and also for the trace ions.
Furthermore, two ED-based technologies were used. SED was utilized to separate chloride
from sulfate ions of an industrial wastewater rich in sodium chloride and sodium sulfate,
achieving separation factors around 80-90 %. EDBM was employed to produce sodium
hydroxide/hydrochloric acid from sodium chloride and sodium hydroxide/sulfuric acid from
sodium sulfate.
Finally, ED, NF and SED were used as pre-treatments for EDBM. With the NF and EDBM
system it was possible to purify the SWRO brine working with NF membranes at 20 bar.
However, the permeate stream was treated by chemical precipitation in order to diminish the
calcium and magnesium concentration before being introduced in the EDBM system.
Maximum NaOH and HCl concentrations of 1 M were obtained. ED was used prior to the
EDBM in order to concentrate the SWRO brine up to 200 gNaCl/L and be able to produce 2
M acid and base. SED was used to separate chloride from sulfate ions of an industrial
wastewater. Both streams, sodium chloride-rich and sodium sulfate-rich were introduced in
the EDBM stack and pure sodium hydroxide, hydrochloric acid (87 %) and sulfuric acid (93 %)
were produced.
Integration of electrically driven membrane separation processes for water treatment and resources recovery
1.1. Challenges on brines and concentrates management: from disposal to valorization for by-products recovery ............................................................... 9
1.2. Electrically driven membrane separation processes using ion-exchange membranes (ED/SED/EDBM) for brines purification and concentration ........ 13
1.3. Integration of membrane technologies as pre-treatment for chemicals production ...................................................................................................... 25
Advantages and benefits Challenges and uncertainties
Surface water discharge to rivers, lakes, ocean, or estuary via a dedicated outfall, or power plant outfall, or blending with wastewater
- Used for facilities of all sizes - Cost effective
- Environmental implications due to the differences in salinity and major ion imbalance between concentrate and ambient surface waters, resulting in adverse impact on aquatic life - Stringent regulations, for example, National Pollutant Discharge Elimination System (NPDES) - Complex and costly permitting
Sewer discharge to an existing wastewater treatment system
- Commonly used for brackish water and wastewater facilities - Low energy use and costs
- Only feasible to small size facilities, limited by the hydraulic capacity of the sewer collection system and by the treatment capacity of the wastewater treatment plant receiving the discharge - May impact the operation of wastewater treatment plant and beneficial use of reclaimed water because of the concentrate salinity and specific constituents, such as sodium, chloride, boron, and bromide in the blended stream due to their potential negative impact on microorganisms, plants, and soil.
Deep well injection into a deep geological formation, that permanently isolates the concentrate from shallower aquifers that may be used as a source of drinking water
- Suitable for inland facilities
- Typically expensive and often used in larger facilities - Requires appropriate geological formation and confined saline water aquifer, not feasible for areas of elevated seismic activity or near geologic faults - Permitting is becoming more stringent because of greater perceived potential for leakage to, and contamination of nearby water supply aquifers
Evaporation ponds
- Suitable for inland and coastal facilities - Easy to implement and low maintenance - Economical if land is inexpensive
- Climate dependent - Large physical footprint - Regulatory permitting may be complicated - Limited to small flows - Need the control of erosion, seepage, and wildlife management
Land application through percolation ponds, or beneficially used for irrigation of lawns, parks, golf courses, or crops
- Relatively easy to implement and low costs - Beneficial use of concentrate
- Limited to irrigation of salt tolerant grass, trees, and plants - Limited to small facilities - Dependent on seasonal irrigation needs and climate - Limited by groundwater protection laws - Potential contamination of soil and groundwater
Thermal zero and near-zero liquid discharge
- Avoid a lengthy and tedious permitting process - Smaller environmental impact - Potential recovery of valuable salts
- Costly, capital and energy intensive - Disposal of the final brine or salt can be expensive - Large carbon footprint
Chapter 1 INTRODUCTION
12
As it can be seen in Table 1, conventional treatments have several disadvantages such as
extensive land use and low productivity. Moreover, these alternatives generate solid salts
and/or liquid waste that require special handling [12]. Thus, investigation on new options to
improve the management of concentrates is a current demand.
Zero liquid discharge (ZLD) or near-ZLD schemes can be used in order to reduce the brine
volume after water recovery for reuse and generation of a dry salt waste or a wet salt waste,
respectively. The main objective of these schemes is to achieve the maximum water
recovery, through several stages of treatment in order to avoid liquid effluent disposal and to
recuperate the valuable compounds from concentrates. ZLD systems combining several
concentration/separation technologies are seen as a promising methodology for inland
desalination. However, these systems are usually expensive and high energy demanding, so
are only partially implemented [13].
Favorable reuse of ED/RO/NF brines represents a promising and sustainable alternative to
other approaches. It is an opportunity to: a) achieve a ZLD scheme strategy that so far has
been applied only on a limited scale because of the large energy needs associated with the
process [14] and b) develop a new paradigm of circular economy concept to transform a
waste to a resource, which is promoted by the EU commission inside the SPIRE program
[15,16].
In the case of industrial brines, there are some potential salts (NaCl, Na2SO4, CaCl2,
MgSO4, NH4Cl, NH4NO3) whose direct reuse in the process itself is usually the most
attractive option as was reported by the Water Supply and Sanitation Technology Platform
Report of Brines Management [17]. However there is a limited demand of this kind of
streams due to its composition. Research and development is still needed to ensure that
the full-scale applications of brine treatment technologies achieve both water treatment
and water and waste recycling. Besides, recycling and valorization of salts are having a
main challenge to develop selective separation technologies and/or combined treatments
in order to enhance the purity of the produced salts. When trying to apply valorization
routes, especially for the NaCl/Na2SO4 mixtures, the desired quality requirements is to
separate onto single concentrated streams of NaCl and Na2SO4 reducing the presence of
other minor ionic or neutral species, and then the main target objective is the separation
of Cl-/SO42-.
Integration of electrically driven membrane separation processes for water treatment and resources recovery
13
For this reason, different membranes technologies have been used in this thesis in order to
valorize these brines, by means of purification, separation, concentration and/or chemical
production from the salt.
1.2. Electrically driven membrane separation processes using ion-exchange membranes (ED/SED/EDBM) for brines purification and concentration
Several separation processes are available for ions separation and fractionation, including
solid-liquid extraction (e.g. ion exchange resins), liquid-liquid extraction (liquid ion exchangers),
[106] A. Efligenir, S. Déon, P. Fievet, C. Druart, N. Morin-Crini, G. Crini, Decontamination of
polluted discharge waters from surface treatment industries by pressure-driven
membranes: Removal performances and environmental impact, Chem. Eng. J. 258
(2014) 309–319.
[107] A. Yaroshchuk, X. Martínez-Lladó, L. Llenas, M. Rovira, J. de Pablo, Solution-
diffusion-film model for the description of pressure-driven trans-membrane transfer of
electrolyte mixtures: One dominant salt and trace ions, J. Memb. Sci. 368 (2011) 192–
201.
[108] A. Yaroshchuk, X. Martínez-Lladó, L. Llenas, M. Rovira, J. de Pablo, J. Flores, et al.,
Mechanisms of transfer of ionic solutes through composite polymer nano-filtration
membranes in view of their high sulfate/chloride selectivities, Desalin. Water Treat. 6
(2009) 48–53.
Chapter 1 INTRODUCTION
34
Integration of electrically driven membrane separation processes for water treatment and resources recovery
35
2. THESIS OVERVIEW
Chapter 2 THESIS OVERVIEW
36
Integration of electrically driven membrane separation processes for water treatment and resources recovery
37
2. Thesis overview
In this work, membrane technologies have been used for water treatment and resources
recovery. Mainly, ED was studied as concentration treatment of the brines in order to produce
NaCl for the chlor-alkali industry (Publication 1). Moreover, modelling was used in order to
understand the behavior of the process (Publication 2). Besides, MVC membranes were
synthetized in order to perform ED experiments (Publication 3).
Furthermore, a purification step was studied by means of NF. Ion rejection by means of NF
was studied by means of different membrane configurations (Publication 4) and the dominant
salt effect on the trace ion rejection was also investigated (Publication 5).
SED was studied to understand its capacity in separating monovalent from divalent anions,
such as Cl- and SO42-. And EDBM was used in order to produce acid and base from its
corresponding salt.
ED, NF and SED have been used as pre-treatments for EDBM. Then, by integration of two of
these membrane processes, it could be possible to pretreat the feed brines and promote
circular economy in the same company. Firstly, NF and EDBM were integrated in order to
purify and produce acid and bases from the brines (Publication 6). Also, ED and EDBM were
used together in order to concentrate the feed brine and then produce acid and base from
them (Publication 7). Finally, SED and EDBM were integrated in order to separate different
charge anions from a high salinity wastewater effluent and to produce acid and base
(Publication 8).
Chapter 2 THESIS OVERVIEW
38
Figure 6. Thesis overview.
Publication 1: Mònica Reig, Sandra Casas, Carlos Aladjem, César Valderrama, Oriol Gibert, Fernando Valero, Carlos Miguel Centeno, Enric Larrotcha, José Luis Cortina. Concentration of NaCl from seawater reverse osmosis brines for the chlor-alkali industry by electrodialysis. Desalination 342, (2014), 107–117
Publication 2: Tanaka, Y., Reig M., Casas S., Aladjem C., Cortina J.L. Computer simulation of ion-exchange membrane electrodialysis for salt concentration and reduction of RO discharged brine for salt production and marine environment conservation. Desalination. 367, (2015), 76-89.
Publication 3: Reig M., Farrokhzad, H., Van der Bruggen, B., Gibert, O., Cortina, J.L. Synthesis of a monovalent selective cation exchange membrane to concentrate reverse osmosis brines by electrodialysis. Desalination. 375, (2015), 1-9
Publication 4: Mònica Reig, Neus Pagès, Edxon Licon, César Valderrama, Oriol Gibert, Andriy Yaroshchuk, José Luis Cortina. Evolution of electrolyte mixtures rejection behaviour
Integration of electrically driven membrane separation processes for water treatment and resources recovery
39
using nanofiltration membranes under spiral wound and flat-sheet configurations. Desalination and water treatment, 56 (13), (2015), 3519-3529.
Publication 5: Mònica Reig, Edxon Licon, Oriol Gibert, Andriy Yaroshchuk, José Luis Cortina. Rejection of ammonium and nitrate from sodium chloride solutions by nanofiltration: Effect of dominant-salt concentration on the trace-ion rejection. Chemical Engineering Journal. 303, (2016), 401–408.
Publication 6: Reig M., Casas S., Gibert, O., Valderrama C., Cortina, J.L. Integration of nanofiltration and bipolar electrodialysis for valorization of seawater desalination brines: Production of drinking and waste water treatment chemicals. Desalination. 382, (2016), 13-20.
Publication 7: M. Reig, S. Casas, C. Valderrama, O. Gibert, J.L. Cortina. Integration of monopolar and bipolar electrodialysis for valorization of seawater reverse osmosis desalination brines: Production of strong acid and base. Desalination, 398, (2016), 87–97.
Publication 8: Mònica Reig, César Valderrama, Oriol Gibert, José Luis Cortina. Selectrodialysis and bipolar membrane electrodialysis combination for industrial process brines treatment: Monovalent-divalent ions separation and acid and base production. Desalination, 399, (2016), 88–95.
Integration of electrically driven membrane separation processes for water treatment and resources recovery
43
3. Objective
The main objective of the current PhD thesis was to study, understand and integrate different membrane technologies for water treatment and resource recovery.
Figure 7. Thesis diagram scheme: membrane integration for resource recovery.
As it is shown in Figure 7, EDBM process has been used as main technology for the
valorization of SWD-RO brines producing acid and base in order to achieve a circular
economy scheme using NF, ED and SED as pre-treatments.
3.1. Specific objectives
The specific objectives were to find optimal operation conditions of the valorization process, to
determine final acid and base concentration and to calculate specific energy consumption
when using pretreatment concentration (ED), purification (NF) or separation (SED) steps to
treat the SWD-RO brines.
Table 3 summarizes the specific objectives depending on the membrane technology studied:
Chapter 3 OBJECTIVE
44
Table 3. Specific objectives depending on the membrane technology.
Membrane technology
Specific objective
ED
- To produce NaCl for the chlor-alkali industry by ED concentration
- To understand the behavior of the process by modelling
- To synthetize cationic monovalent selective membranes
NF
- To understand ion rejection by means of different membrane configurations
- To study the dominant salt effect on the trace ion rejection
SED - To quantify the capacity in separating monovalent from divalent ions
- To evaluate the best initial product composition and concentration
EDBM - To produce acid and base from its corresponding salt
- To estimate the NaOH, HCl and H2SO4 concentration reached
Membrane technology integration
NF + EDBM - To purify brines and produce acid and base
ED + EDBM - To concentrate brines and produce acid and base
SED + EDBM - To separate different charge ions from wastewater and produce acid and base
Integration of electrically driven membrane separation processes for water treatment and resources recovery
4-11 PUBLICATIONS
Chapters 4 to 11 of the thesis contain the magazine articles cited in the list. For respecting the rights of the publisher, you should consult them on your website Chapter 4, Publication 1:
M. Reig, S. Casas, C. Aladjem, et al. Concentration of NaCl from seawater reverse osmosis brines for the chlor-alkali industry by electrodialisys. Desalination, vol. 342, 2014, p. 107-117 Doi: 10.1016/j.desal.2013.12.021 http://www.sciencedirect.com/science/atyicle/pii/S0011916413006073
Chapter 5, Publication 2:
Y.Tanaka, M.Reig, S.Casas, et al. Computer simulation of ion-exchange membrane electrodialysis for salt concentration and reduction of RO discharged brine for salt production and marine environment concentration. Desalination, vol. 367, 2015, p.76-89 Doi: 10.1016/j.desal2015.03.022 http://www.sciencedirect.com/science/article/pii/S001196415001897
Chapter 6, Publication 3:
M. Reig, H Farrokhzad, B.Van der Bruggen, et al. Synthesis of a monovalent selective cation exchange membrane to concentrate reverse osmosis brines by electrodialysis. Desalination vol.375, 2 Nov. 2015, p.1-9 Doi: 10.1016/j.desal.2015.07.023 http://www.sciencedirect.com/science/article/pii/S001191641530031X
Chapter 7, Publication 4:
M. Reig, N. Pagès, E. Licon, et al. Evolution of electrolyte mixtures rejection behaviour using nanofiltration membranes under spiral wound and flat-sheet configurations. Desalination and Water Treatment vol.56, 2015 #13. Doi: 10.1080/19443994.2014.974215 http://www.tandfonline.com/doi/full/10.1080/19443994.2014.974215
Chapter 8, Publication 5:
M. Reig, E. Licon, O. Gibert. Rejection of ammonium and nitrate from sodium chloride solutions by nanofiltration: Effect of dominant-salt concentration on the trace-ion rejection. Chemical Engineering Journal vol. 303, 1 Nov 2016, p. 401-408 Doi: 10.1016/j.cej.2016.06.025 http://www.sciencedirect.com/science/article/pii/S1385894716308324
M. Reig, S. Casas, O. Gibert, et al. Integration of nanofiltration and bipolar electrodialysis for valorization of seawater desalination brines: Production of drinking and waste wàter treatment chemicals. Desalination 382 (2016) 13–20 Doi: 10.1016/j.desal.2015.12.013 http://www.sciencedirect.com/science/article/pii/S001191641530148X
Chapter 10, Publication 7:
M. Reig , S. Casas, C. Valderrama, et al. Integration of monopolar and bipolar electrodialysis for valorization of seawater reverse osmosis desalination brines: Production of strong acid and base. Desalination, vol. 398, 15 November 2016, p. 87-97 Doi: 10.1016/j.desal.2016.07.024 http://www.sciencedirect.com/science/article/pii/S0011916416308591
Chapter 11, Publication 8:
M. Reig, C. Valderrama, O. Gibert, et al. Selectrodialysis and bipolar membrane electrodialysis combination for industrial process brines treatment: Monovalent-divalent ions separation and acid and base production. Desalination vol. 399, 1 December 2016, p. 88-95 Doi: 10.1016/j.desal.2016.08.010 http://www.sciencedirect.com/science/article/pii/S0011916416303587